Azo-dyestuff of the anthraquinone series



Patented Jan. 6, 1931 TENT f pm BEBTRAM MAYER, on BASEIQ, enn mooswiinstnn, or isrnunwnnr, nnaajsssnn, Y SWITZERLAND, nssrernons To sccI rY or CHEMICAL INDUSTRY n BASIJE, or

BASEL, SWITZERLAND AZO DYES'TU-F-F :or Ame-memes sum Es No Drawing'. llpplication fi led March ear s29, Serial ir /$0,437, and in Switzerland spin 4, 1928,

The present invention relates to the manufacture of new azo-dyestufis of the anthraquinone series particularly suitable for. the dyeing of esters and others of the cellulose. It comprises the new products, the method of making same, and the material dyed with the new dyestuffs. I p

It has been found that new dyestuli's are obtained by diazotizing a compound of the general formlua in which-K is an iuisulfonated residue of any coupling componentand as in twocases hydrogen and in the third NHR .(R=hydrogen or alkyl). H

The new dyestuffs are intensely colored powders insoluble in water and which dissolye in concentrated sulfuric acidto characteristic solutions the color of which mayvary from green-olive via yellow, yellow-brown to redbrown and red-violet. They are valuable producing fast tints on cellulose derlvatlves, such ascelluloseesters or others, whether applied to these in theiform oftextiles (acetate silk or thelike) or of :artificial masses (cellu 'loid, Zapon lacquers or the like). The shades of these tints are orange to red, v1olet or brown.

For dyeing textiles it is ad antageous to treat the dyestufl' before dyeing with a suit able dispersing agent so as to bringit into the form of paste. Such paste may also be converted into solid preparations by cautious evaporation. '7 i 1 As coupling components there come into question allgthe usual unsulfonated coupling components, such as inter alia compounds which have a methylene group capable of reaction, suchas derivatlvesofthe aceto-acetic acid (for example pyrazolones); phenols,

such asphenol, cresols, resoreinol, or the like; naphthols, such as 00- and ,8-n aphthol amines, such as dialkyLanilineS, meta-phenylenedi amine, meta-toluylenediamine, oaand ,8-naphthylamines, N-alkyl derivatives thereof, and the like. 7

Particularly valuable are the red to violet dyestuffs in which K is the residue of a socalled yellow component, such as a pyrazolone, a phenol, a cresol and r'esorcinol, and n whichthe as standing mthe 2nd S- position are hydrogen and the a; in thee-position .is an NH: group.

The following examples illustrate the invention, .the parts beingby wei ht Example 1 12,1 parts of 1-amino-L-methylaniinoantliraquinoue are suspended in 100 parts of sulfuric acid of 10 .per .cent. strength, and there are added graduallyat room temperature an aqueous solution of 3,4 parts of sodiumnitrite. Stirring is continued until the dried or directly converted into a paste.

E ammple 2 13.5 parts of 1: S-aminonitroanthraquinone are dissolved in 135 parts of sulfuric acid monohydrate and the solution is mixed at a temperature below 20 C. with 3,6 parts of sodium nitrite and stirred at room tempera ture until the nitrous acid has disappeared, or is present only in traces. The whole is then poured upon 400 parts of ice, the diazobody which separates is filtered by suction and introduced. into an aqueous solution of 6 parts of resorcinol containing excess of sodium carbonate. The coupling is quickly completed.

The new dyestufi is precipitated .in the form of orange, insoluble flocks; these are filtered and washed.

The dyestuif thus obtained is introduced while stirring well into a solution of 6 parts of sodium hydrosulfide in 200 parts of water and stirring is continued for about hour to 1 hour at 5060 (3., whereby the nitrogroup is reduced. The separated amino-alodyestuff of the probable formula The procedure is similar with other anthraquinone derivatives and coupling compo- Ewample 3 .15 parts of the product of the reduced dyestuif of Example 2 (best in the form of a freshly made press-cake) are stirred in known manner with sulfite cellulose waste liquor or with a sulfonation productof the distillation residue from benz'aldehyde or turpentine oil, so as to form a uniform paste 01": 20 percent. strength.

I 5 parts of this paste'are stirred with about the same quantity of a soap solution oi 6 per cent. strength at about 50 C. and diluted to form 300 parts with lukewarm water. 10 parts of acetate silk are enteredinto this bath which is then heated within, A hour to 80 (1.; the goods are handled atthis temperature for about hour. They are then rinsed and dried. The acetate silk is dyed beautiful reddish orange tints.

Example 4 4 to 5 parts of the reduced dyestufl from Properties of the azo-dyestull (in some cases after reduction or sapoui- V fication Diazotizcd-componcnt oupling-i-oiupermit V t Color of solution in Color tint obtained 001m of puwlu concentrated H2S04 on acetate silk I 1:4-amino-nitroauthraqui- Resorcinol" Black'violetn'. Brownish-scarlet Pure violet.

m-toluylene-diaminq" Brown-violet Orange-brown." Reddish violet. l-naphthylamine i et Olive-grcen Violet. V Q-naphthol do Olive-brown Reddish-violet. Phenyl-methyl-pyrazolonc do Orange-brown Red-violet.

VI 1:5-aminonitroanthraqui- Resorcinol Brown-orange"; Deep-orange Reddish-orauge.

none. VII do l\/I cta-toluylenediamine...- Red-or Yellow V Reddish-orange. VIII do Diethylaniline Br0wn-red Brown-orange Brown-orange.

IX 1:8-aminonltroanthraqui- Rcsorcinol Redm; Q. Yellow Orange re'd.

L'Ieta-toluylene-diamine i Orange red. 2-naphthol '01 Orange red. Phenylmetl y Yello Orange red. Diethylamline r. Yellow-brown. Orange red.

XIV l-amino-2-methyl-4-nitroan Resorcinol Yellow-brown Reddish-violet;

thraquinonc. v XV do lVIeta-toluylcne-dxaminc do Currant. XVI do Phenylmethyl-pyrazolone-r. .do Violet. V

XVII l-amino l-methyl-amino-an- Meta-toluylene-diamine Brown-black Sa1mon-red Violet-brown.

thraquinone. I XVIII do l-naphthylamme Violet-brown Dull-violet; Reddish-brown.

XIX l-amino-i-cyclohexylami- Phenylmethyl-pyrazolone-., Blackish Red-violet .i Brown.

noanthraquinone. w

The formula of the dyestuif Iis veryprobably: Y

.| V 0 KB: 7

The formula of the dyestuff III is very probably;

g) ITI=N NH,

I O NH:

The formula of the dyestuff XIV is very probably:

N=N-- -on' A -0Hi on.

O NIT-2 The formula of the dyestuff XIX is very probably:

vVhat we claim is: 1. As new products the unsulfonated azodyestuffs of the general formula in which K stands for a residue of any coupling component and w in two cases for hydrogen and in the third for which products form intensely colored powders which dissolve in concentrated sulfuric acid with colorations the tints of which may vary from green-olive via yellow; yellow-brown to red-brown and red-violet, and

(R=hydrogen or alkyl),

which dye acetate silk orange to red, violet and brown tints. V

2. As new products the unsulfonated azodyestuffs of the general formula l o NHR in which K stands for a residue of any coupling component and R for hydrogen or alkyl, which products form intensely colored powders which dissolve in concentrated sulfuric acid with colorations the tints of which may vary from green-olive via yellow, yellow-brown to red-brown and red-violet, and which dye acetate silk orange to red, violet and brown tints. I

3. As new products the unsulfonated azodyestuffs of the general formula in which K is a residue of a so-called yellowcomponent, which products form-dark violet powders dissolving in concentrated sulfuric acid with red-brown to orange-brown coloration, and dyeing acetate silk red to violet tints.

4. As a new product the azo-dyestuffs of the probable formula of claim 3.

8. The materials dyed with the dyestuffs of claim 4.

In witness whereof we have hereunto signed our names this 12th day of March,

BERTRAM MAYER. JACOB WURGLER. 

